Enzymatic detergent compositions inhibiting dye transfer

ABSTRACT

The present invention relates to inhibiting dye transfer compositions comprising polyamine N-oxide polymers which contain units having the following structure formula: ##STR1## wherein P is a polymerizable unit, whereto the N--group can be attached to or wherein the N--O group forms part of the polymerizable unit or a combination of both. ##STR2##  R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N--O group can be attached or wherein the nitrogen of the N--O group form part of these groups.

FIELD OF THE INVENTION

The present invention relates to dye transfer inhibiting compositionscontaining enzymes. More in particular, this invention relates to dyetransfer inhibiting compositions comprising polyamine N-oxide containingpolymers and enzymes.

BACKGROUND OF THE INVENTION

Detergent compositions containing enzymes are well known in art. It isequally well recognized that enzyme deactivation occurs in detergentcompositions formulated with enzymes. The loss of detergent activity ofenzymes is among others depending on the presence of adjunct detergentingredients.

One type of adjunct detergent ingredient that is added to detergentingredients are dye transfer inhibiting polymers. Said polymers areadded to detergent compositions in order to inhibit the transfer of dyesfrom colored fabrics onto other fabrics washed therewith. These polymershave the ability to complex or adsorb the fugitive dyes washed out ofdyed fabrics before the dyes have the opportunity to become attached toother articles in the wash.

Copending European Patent Application No. 92202168.8 describes polyamineN-oxide containing polymers which are very efficient in eliminatingtransfer of solubilized or suspended dyes. It has now been surprisinglyfound that certain polyamine N-oxide polymers provide a stabilizingeffect for enzymes formulated in detergent compositions.

In addition to this stabilizing effect, the dye transfer inhibitingperformance of the polyamine N-oxide containing polymers are enhanced bythe addition of certain type of enzymes. This finding allows toformulate detergent compositions which exhibit excellent dye transferinhibiting properties while maintaining excellent enzyme activity.

According to another embodiment of this invention a process is alsoprovided for laundering operations involving colored fabrics.

Polymers have been used within detergent compositions to inhibit dyetransfer. EP-A-O 102 923 describes the use of carboxyl containingpolymers within an aqueous compositions. DE-A-2 814 329 discloses theuse of N-vinyl-oxazolidone polymers and FR-A-2 144 721 discloses the useof 15-35% of a copolymer of polyvinylpyrrolidone and acrylic acidnitrile or maleic anhydride within a washing powder. EP-265 257describes detergent compositions comprising an alkali-metalcarboxy-metal carboxymethylcellulose, a vinylpyrrolidone polymer and apolycarboxylate polymer.

SUMMARY OF THE INVENTION

The present invention relates to inhibiting dye transfer compositionscomprising

a) a polymer selected from polyamine N-oxide containing polymers whichcontain units having the following structure formula: ##STR3## wherein Pis a polymerisable unit, whereto the N--O group can be attached to orwherein the N--O group forms part of the polymerisable unit. ##STR4## Rare aliphatic, ethoxylated aliphatic, aromatic, heterocyclic oralicyclic groups whereto the nitrogen of the N--O group can be attachedor wherein the nitrogen of the N--O group is part of these groups.

b) an enzyme.

DETAILED DESCRIPTION OF THE INVENTION

The compositions of the present invention comprise as an essentialelement a polymer selected from polyamine N-oxide containing polymerswhich contain units having the following structure formula (I): ##STR5##wherein P is a polymerisable unit, whereto the R--N--O group can beattached to or wherein the R--N--O group forms part of the polymerisableunit or a combination of both. ##STR6## R are aliphatic, ethoxylatedaliphatics, aromatic, heterocyclic or alicyclic groups or anycombination thereof whereto the nitrogen of the N--O group can beattached or wherein the nitrogen of the N--O group is part of thesegroups

The N--O group can be represented by the following general structures:##STR7## wherein R1, R2, R3 are aliphatic groups, aromatic, heterocyclicor alicyclic groups or combinations thereof, x or/and y or/and z is 0 or1 and wherein the nitrogen of the N--O group can be attached or whereinthe nitrogen of the N--O group forms part of these groups.

The N--O group can be part of the polymerisable unit (P) or can beattached to the polymeric backbone or a combination of both.

Suitable polyamine N-oxides wherein the N--O group forms part of thepolymerisable unit comprise polyamine N-oxides wherein R is selectedfrom aliphatic, aromatic, alicyclic or heterocyclic groups. One class ofsaid polyamine N-oxides comprises the group of polyamine N-oxideswherein the nitrogen of the N--O group forms part of the R-group.Preferred polyamine N-oxides are those wherein R is a heterocyclic groupsuch as pyridine, pyrrole, imidazole, pyrrolidine, piperidine, quinolineand derivatives thereof. Another class of said polyamine N-oxidescomprises the group of polyamine N-oxides wherein the nitrogen of theN--O group is attached to the R-group.

Other suitable polyamine N-oxides are the polyamine oxides whereto theN--O group is attached to the polymerisable unit. Preferred class ofthese polyamine N-oxides are the polyamine N-oxides having the generalformula (I) wherein R is an aromatic, heterocyclic or alicyclic groupswherein the nitrogen of the N--O functional group is part of said Rgroup. Examples of these classes are polyamine oxides wherein R is aheterocyclic compound such as pyridine, pyrrole, imidazole andderivatives thereof.

Another preferred class of polyamine N-oxides are the polyamine oxideshaving the general formula (I) wherein R are aromatic, heterocyclic oralicyclic groups wherein the nitrogen of the N--O functional group isattached to said R groups. Examples of these classes are polyamineoxides wherein R groups can be aromatic such as phenyl.

Any polymer backbone can be used as long as the amine oxide polymerformed is water-soluble and has dye transfer inhibiting properties.Examples of suitable polymeric backbones are polyvinyls, polyalkylenes,polyesters, polyethers, polyamide, polyimides, polyacrylates andmixtures thereof.

The amine N-oxide polymers of the present invention typically have aratio of amine to the amine N-oxide of 10:1 to 1:1000000. However theamount of amine oxide groups present in the polyamine N-oxide containingpolymer can be varied by appropriate co-polymerization or by appropriatedegree of N-oxidation. Preferably, the ratio of amine to amine N-oxideis from 2:3 to 1:1000000. More preferably from 1:4 to 1:1000000, mostpreferably from 1:9 to 1:1000000. The polymers of the present inventionactually encompass random or block copolymers where one monomer type isan amine N-oxide and the other monomer type is either an amine N-oxideor not. The amine oxide unit of the polyamine N-oxides has a PKa<10,preferably PKa<7, more preferred PKa<6.

The polyamine N-oxide containing polymers can be obtained in almost anydegree of polymerisation. The degree of polymerisation is not criticalprovided the material has the desired water-solubility anddye-suspending power. Typically, the average molecular weight of thepolyamine N-oxide containing polymers is within the range of 500 to1000,000; preferably from 1000 to 30000, more preferably from 3000 to20000, most preferably from 5000 to 15000.

The polyamine N-oxide containing polymers of the present invention aretypically present from 0.001% to 10%, more preferably from 0.05% to 1%,most preferred from 0.05% to 0.5% by weight of the dye transferinhibiting composition. The present compositions are conveniently usedas additives to conventional detergent compositions for use in laundryoperations. The present invention also encompasses dye transferinhibiting compositions which will contain detergent ingredients andthus serve as detergent compositions.

Methods for making polyamine N-oxides:

The production of the polyamine-N-oxide containing polymers may beaccomplished by polymerizing the amine monomer and oxidizing theresultant polymer with a suitable oxidizing agent, or the amine oxidemonomer may itself be polymerized to obtain the polyamine N-oxide.

The synthesis of polyamine N-oxide containing polymers can beexemplified by the synthesis of polyvinyl-pyridine N-oxide.Poly-4-vinylpyridine ex Polysciences (mw. 50 000, 5.0 g., 0.0475 mole)was predisolved in 50 ml acetic acid and treated with a peracetic acidsolution (25 g of glacial acetic acid, 6.4 g of a 30% vol. solution ofH₂ O₂, and a few drops of H₂ SO₄ give 0.0523 mols of peracetic acid) viaa pipette. The mixture was stirred over 30 minutes at ambienttemperature (32 C.). The mixture was then heated to 80-85 C. using anoil bath for 3 hours before allowing to stand overnight. The polymersolution then obtained is mixed with 11 of acetone under agitation. Theresulting yellow brown viscous syrup formed on the bottom is washedagain with 11 of aceton to yield a pale crystalline solid.

The solid was filtered off by gravity, washed with aceton and then driedover P₂ O₅.

The amine : Amine N-oxide ratio of this polymer is 1:4 (determined byNMR).

ENZYMES

The enzymes which are to be included in the detergent formulations aredetersive enzymes which can be used for a wide variety of purposesincluding removal of protein-based, carbohydrate-based, ortriglyceride-based stains, for example, and prevention of refugee dyetransfer. The enzymes to be incorporated include proteases, amylases,lipases, cellulases, and peroxidases, as well as mixtures thereof. Othertypes of enzymes may also be included. The enzymes may be of anysuitable origin, such as vegetable, animal, bacterial, fungal and yeastorigin. However, their choice is governed by several factors such aspH-activity and/or stability optima, thermostability, stability versusactive detergents, builders and so on. In this respect bacterial orfungal enzymes are preferred, such as bacterial amylases and proteases,and fungal cellulases.

Enzymes are normally incorporated at levels sufficient to provide up toabout 5 mg by weight, more typically about 0.05 mg to about 3 mg, ofactive enzyme per gram of the composition.

Cellulase:

The cellulases usable in the present invention include both bacterial orfungal cellulase. Preferably, they will have a pH optimum of between 5and 9.5. Suitable cellulases are disclosed in U.S. Pat. No. 4,435,307,which discloses fungal cellulase produced from Humicola insolens.Suitable cellulases are also disclosed in GB-A-2.075.028 ;GB-A-2.095.275 and DE-OS-2.247.832.

Examples of such cellulases are cellulases produced by a strain ofHumicola insolens (Humicola grisea var. thermoidea), particularly theHumicola strain DSM 1800, and cellulases produced by a fungus ofBacillus N or a cellulase 212-producing fungus belonging to the genusAeromonas, and cellulase extracted from the hepatopancreas of a marinemollusc (Dolabella Auricula Solander). Other suitable cellulases arecellulases originated from Humicola Insulens having a molecular weightof about 50 KDa, an isoelectric point of 5.5 and containing 415 aminoacids. Such cellulase are described in Copending European patentapplication No. 93200811.3 Especially suitable cellulase are thecellulase having color care benefits. Examples of such cellulases arecellulase described in European patent application No. 91202879.2,Carenzyme (Novo). It has been found that cellulase enhances considerablythe efficiency of polyamine N-oxide containing polymers in terms ofcolor appearance.

Protease:

Suitable examples of proteases are the subtilisins which are obtainedfrom particular strains of B. subtilis and B. licheniforms. Proteolyticenzymes suitable for removing protein-based stains that are commerciallyavailable include those sold under the tradenames Alcalase , Savinaseand Esperase by Novo Industries A/S (Denmark) and Maxatase byInternational Bio-Synthetics, Inc. (The Netherlands) and FN-base byGenencor, Optimase and opticlean by MKC.

Of interest in the category of proteolytic enzymes, especially forliquid detergent compositions, are enzymes referred to herein asProtease A and Protease B. Protease A and methods for its preparationare described in European Patent Application 130,756. Protease B is aproteolytic enzyme which differs from Protease A in that it has aleucine substituted for tyrosine in position 217 in its amino acidsequence. Protease B is described in European Patent Application SerialNo. 87303761.8. Methods for preparation of Protease B are also disclosedin European Pat. Application 130,756.

Amylase

Amylases include, for example, amylases obtained from a special strainof B. licheniforms, described in more detail in British PatentSpecification No. 1,296,839 (Novo). Amylolytic proteins include, forexample, Rapidase, Maxamyl (International Bio-Synthetics, Inc.) andTermamyl,(Novo Industries).

Lipase:

Suitable lipase enzymes for detergent usage include those produced bymicroorganisms of the Pseudomonas group, such as Pseudomonas stutzeriATCC 19.154, as disclosed in British Patent No. 1,372,034. Suitablelipases include those which show a positive immunoligical cross-reactionwith the antibody of the lipase, produced by the microorganismPseudomonas fluorescent IAM 1057. This lipase and a method for itspurification have been described in Japanese Patent Application53-20487. This lipase is available from Amano Pharmaceutical Co. Ltd.,Nagoya, Japan, under the trade name Lipase P "Amano," hereinafterreferred to as "Amano-P". Such lipases of the present invention shouldshow a positive immunological cross reaction with the Amano-P antibody,using the standard and well-known immunodiffusion procedure according toOuchterlony (Acta. Med. Scan., 133, pages 76-79 (1950)). These lipases,and a method for their immunological cross-reaction with Amano-P, arealso described in U.S. Pat. No. 4,707,291. Typical examples thereof arethe Amano-P lipase, the lipase ex Pseudomonas fragi FERM P 1339(available under the trade name Amano-B), lipase ex Pseudomonasnitro-reducens var. lipolyticum FERM P 1338 (available under the tradename Amano-CES), lipases ex Chromobacter viscosum, e.g. Chromobacterviscosum var. lipolyticum NRRLB 3673, commercially available from ToyoJozo Co., Tagata, Japan; and further Chromobacter viscosum lipases fromU.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, andlipases ex Pseudomonas gladioli. Especially suitable Lipase are lipasesuch as M1 Lipase (Ibis) and Lipolase (Novo).

Peroxidase:

Peroxidase enzymes are used in combination with oxygen sources, e.g.percarbonate, perborate, persulfate, hydrogen peroxide, etc They areused for "solution bleaching", i.e. to prevent transfer of dyes ofpigments removed from substrates during wash operations to othersubstrates in the wash solution. Peroxidase enzymes are known in theart, and include, for example, horseradish peroxidase, ligninase, andhaloperoxidase such as chloro- and bromo-peroxidase.Peroxidase-containing detergent compositions are disclosed, for example,in PCT Internation Application WO 89/099813, published October 19, 1989,by O. Kirk, assigned to Novo Industries A/S, and in European Patentaplication No. 91202882.6.

The peroxidases which may be employed for the present purpose may beisolated from and are producible by plants (e.g. horseradish peroxidase)or micororganisms such as fungi or bacteria. Some preferred fungiinclude strains belonging to the subdivision Deuteromycotina, classHypho-mycetes, e.g. Fusarium, Humicola, Tricoderma, Myrothecium,Verticillum, Arthromyces, Caldariomyces, Ulocladium, Embellisia,Cladosporium or Dreschlera, in particular Fusarium oxysporum (DSM 2672),Humicola insolens, Tricho-derma resii, Myrothecium verrucana (IFO 6113),Verticilluum alboatrum, Verticillum dahlie, Arthromyces ramosus (FERMP-7754), Caldariomyces fumago, Ulocladium chartarum, Embellisia alliorDreschlera halodes.

Other preferred fungi include strains belonging to the subdivisionBasidiomycotina, class Basidiomycetes, e.g. Coprinus, Phanerochaete,Coriolus or Trametes, in particular Coprinus cinereus f. microsporus(IFO 8371), Coprinus macrorhizus, Phanerochaete chrysosporium (e.g.NA-12) or Coriolus versicolor (e.g. PR4 28-A).

Further preferred fungi include strains belonging to the subdivisionZygomycotina, class Mycoraceae, e.g. Rhizopus or Mucor, in particularMucor hiemalis.

Some preferred bacteria include strains of the order Actinomycetales,e.g. Streptomyces spheroides (ATTC 23965), Streptomyces thermoviolaceus(IFO 12382) or Strep-toverticillum verticillium ssp. verticillium.

Other preferred bacteria inlude Bacillus pumillus (ATCC 12905), Bacillusstearothermophilus, Rhododbacter sphae-roides, Rhodomonas palustri,Streptococcus lactis, Pseudomonas purrocinia (ATCC 15958) or Pseudomonasfluorescens (NRRL B-11).

Other potential sources of useful peroxidases are listed in B. C.Saunders et al., op. cit., pp. 41-43.

Methods of producing enzymes to be used according to the invention aredescribed in the art, cf. for example FEBS Letters 1625, 173(1), Appliedand Environmental Micro-biology, Feb. 1985, pp. 273-278, AppliedMicrobiol. Bio-technol. 26, 1987, pp. 158-163, Biotechnology Letters9(5), 1987, pp. 357-360, Nature 326, Apr. 2, 1987, FEBS Letters 4270,209(2), p.321, EP 179 486, EP 200 565, GB 2 167 421, EP 171 074, andAgric. Biol. Chem. 50(1), 1986, p. 247.

Particularly preferred peroxidases are those which are active at thetypical pH of washing liquors, i.e. at a pH of 6.5-10.5, preferably6.5-9.5, and most preferably 7.5-9.5. Such enzymes may be isolated byscreening for the relevant enzyme production by alkalophilicmicroorganisms, e.g. using the ABTS assay described in R. E. Childs andW. G. Bardsley, Biochem. J.145, 1975, pp. 93-103.

Other preferred peroxidases are those which exhibit a goodthermostability as well as a good stability towards commonly useddetergent components such as non-ionic, cat-ionic, or anionicsurfactants, detergent builders, phos-phate etc.

Another group of useful peroxidases are haloperoxidases, such as chloro-and bromoperoxidases.

The peroxidase-enzyme may futhermore be one which is producible by amethod comprising cultivating a host cell transformed with a recombinantDNA vector which carries a DNA sequence encoding said enzyme as well asDNA sequences encoding functions permitting the expression of the DNAsequence encoding the enzyme, in a culture medium under conditionspermitting the expression of the enzyme and recovering the enzyme fromthe culture.

A DNA fragment encoding the enzyme may, for instance, be isolated byestablishing a cDNA or genomic library of a microorganism producing theenzyme of interest, such as one of the organisms mentioned above, andscreening for positive clones by conventional procedures such as byhybridization to oligonucleotide probes synthesized on the basis of thefull or partial amino acid sequence of the enzyme, or by selecting forclones expressing the appropriate enzyme activity , or by selecting forclones producing a protein which is reactive with an antibody againstthe native enzyme.

Once selected, the DNA sequence may be inserted into a suitablereplicable expression vector comprising appropriate promotor, operatorand terminator sequences permitting the enzyme to be expressed in aparticular host organism, as well as an origin of replication, enablingthe vector to replicate in the host organism in question.

The resulting expression vector may then be transformed into a suitablehost cell, such as a fungal cell, preferred examples of which are aspecies of Aspergillus, most preferably Aspergillus oryzae orAspergillus niger. Fungal cells may be transformed by a processinvolving protoplast formation and transformation of the protoplastsfollowed by regeneration of the cell wall in a manner known per se. Theuse of Aspergillus as a host micororganism is described in EP 238,023(of Novo Industri A/S).

Alternatively, the host organisms may be a bacterium, in particularstrains of Streptomyces and Bacillus, or E. coli. The transformation ofbacterial cells may be performed according to conventional methods, e.g.as described in T. Maniatis et al., Molecular Cloning: A LaboratoryManual, Cold Spring Harbor, 1982.

The screening of appropriate DNA sequences and construction of vectorsmay also be carried out by standard procedures, cf. T. Maniatis et al.,op. cit.

The medium used to cultivate the transformed host cells may be anyconventional medium suitable for growing the host cells in question. Theexpressed enzyme may conveniently be secreted into the culture mediumand may be recovered therefrom by well-known procedures includingseparating the cells from the medium by centrifugation or filtration,precipitating proteinaceous components of the medium by means of a saltsuch as ammonium sulphate, followed by chromatographic procedures suchas ion exchange chromatography, affinity chromatography, or the like.

The screening of appropriate DNA sequences and construction of vectorsmay also be carried out by standard procedures, cf. T. Maniatis et al.,op. cit.

The medium used to cultivate the transformed host cells may be anyconventional medium suitable for growing the host cells in question. Theexpressed enzyme may conveniently be secreted into the culture mediumand may be recovered therefrom by well-known procedures includingseparating the cells from the medium by centrifugation or filtration,precipitating proteinaceous components of the medium by means of a saltsuch as ammonium sulphate, followed by chromatographic procedures suchas ion exchange chromatography, affinity chromatography, or the like.

At the beginning or during the process, H₂ O₂ may be added, e.g. in anamount of 0.001-5 mM, particularly 0.01-1 mM. When using Coprinusperoxidase, 0.01-0.25 mM H₂ O₂ is preferred, and with B. pumilusperoxidase 0.1-1 mM H₂ O₂.

The hydrogen peroxide may be added as hydrogen peroxide or a precursorthereof, preferably a perborate or percarbonate. The level of hydrogenperoxide precursor that can be used is dependent on the specificproperties of the peroxidase chosen, e.g. Coprinus peroxidase should beapplied in a detergent composition which contains less than 5%perborate.

In the process of this invention, it may be desirable to utilize anenzymatic process for hydrogen peroxide formation. Thus, the processaccording to the invention may additionally comprise adding an enzymaticsystem (i.e. an enzyme and a substrate therefore) which is capable ofgenerating hydrogen peroxide at the beginning or during the washingand/or rinsing process.

One such category of hydrogen peroxide generating systems comprisesenzymes which are able to convert molecular oxygen and an organic orinorganic substrate into hydrogen peroxide and the oxidized substraterespectively. These enzymes produce only low levels of hydrogenperoxide, but they may be employed to great advantage in the process ofthe invention as the presence of peroxidase ensures an efficientutilization of the hydrogen peroxide produced.

Preferred hydrogen peroxide-generating enzymes are those which act oncheap and readily available substrates which may conveniently beincluded into detergent compositions. An example of such a substrate isglucose which may be utilized for hydrogen peroxide production by meansof glucose oxidase. Suitable oxidases include those which act onaromatic compounds such as phenols and related substances, e.g. catecholoxidases, laccase. Other suitable oxidases are urate oxidase, galactoseoxidase, alcohol oxidases, amine oxidases, amino acid oxidase,amyloglucosidase, and cholesterol oxidase.

The preferred enzymatic systems are alcohol and aldehyde oxidases.

The more preferred systems for granular detergent application would havesolid alcohols, e.g. glucose whose oxidation is catalysed by glucoseoxidase to glucoronic acid with the formation of hydrogen peroxide.

The more preferred systems for liquid detergent application wouldinvolve liquid alcohols which could also act as, for example, solvents.An example is ethanol/ethanol oxidase.

The quantity of oxidase to be employed in compositions according to theinvention should be at least sufficient to provide a constant generationof 0.01 to 10 ppm AvO per minute in the wash. For example, with theglucose oxidase, this can be achieved at room temperature and at pH 6 to11, preferentially 7 to 9 with 50-5000 U/1 glucose oxidase, 0.005 to0.5% glucose under constant aeration.

The addition of another oxidisable substrate for the peroxidase at thebeginning or during the washing and/or rinsing process may enhance thedye transfer inhibitory effect of the peroxidase employed. This isthought to be ascribable to the formation of short-lived radicals orother oxidised states of this substrate which participate in thebleaching or other modification of the coloured substance. Examples ofsuch oxidisable substrates are metal ions, e.g. Mn⁺⁺, halide ions, e.g.chloride or bromide ions, or organic compounds such as phenols, e.g.p-hydroxycinnamic acid or 2,4-dichlorophenol. Other examples of phenoliccompounds which may be used for the present purpose are those given inM. Kato and S. Shimizu, Plant Cell Physiol. 26(7), 1985, pp. 1291-1301(cf. Table 1 in particular) or B.C. Saunders et al., op. cit., p. 141ff. The amount of oxidisable substrate to be added is suitably betweenabout 1 μM and 1 mM.

In the process of the invention, the peroxidase will typically be addedas a component of a detergent composition and may be added in an amountof 0.01-100 mg enzyme per liter of wash liquid. As such, it may beincluded in the detergent composition in the form of a non-dustinggranulate, a liquid, in particular a stabilized liquid, or a protectedenzyme. Non-dusting granulates may be produced, e.g. as disclosed inU.S. Pat. Nos. 4,106,991 and 4,661,452 (both to Novo Industri A/S) andmay optionally be coated by methods known in the art. Liquid enzymepreparations may, for instance, be stabilized by adding a polyol such aspropylene glycol, a sugar or sugar alcohol, lactic acid or boric acidaccording to established methods. Other enzyme stabilizers are wellknown in the art. Protected enzymes may be prepared according to themethod disclosed in EP 238,216. The detergent composition may alsocomprise one or more substrates for the peroxidase. Usually, the pH of asolution of the detergent composition of the invention will bepreferably from 7-12, especially from 7.5 to 9.5. The wash pH isdependent on the peroxidase chosen, e.g. Coprinus peroxidase should beapplied in a wash pH below 9.5. It has been found that peroxidasesenhance considerably the efficiency of polyamine N-oxide containingpolymers in terms of dye transfer inhibition.

A wide range of enzyme materials and means for their incorporation intosynthetic detergent granules is also disclosed in U.S. Pat. No.3,553,139. Enzymes are further disclosed in U.S. Pat. No. 4,101,457,Place et al, issued Jul. 18, 1978, and in U.S. Pat. No. 4,507,219,Hughes, issued Mar. 26, 1985, both incorporated herein by reference.Enzyme materials useful for liquid detergent formulations, and theirincorporation into such formulations, are disclosed in U.S. Pat. No.4,261,868, Hora et al, issued Apr. 14, 1981.

For granular detergents, the enzymes are preferably coated or prilledwith additives inert toward the enzymes to minimize dust formation andimprove storage stability. Techniques for accomplishing this arewell-known in the art. In liquid formulations, an enzyme stabilizationsystem is preferably utilized. Enzyme stabilization techniques foraqueous detergent compositions are well known in the art. For example,one technique for enzyme stabilization in aqueous solutions involves theuse of free calcium ions from sources such as calcium acetate, calciumformate and calcium propionate. Calcium ions can be used in combinationwith short chain carboxylic acid salts, preferably formates. See, forexample, U.S. Pat. No. 4,318,818. It has also been proposed to usepolyols like glycerol and sorbitol. Alkoxy-alcohols, dialkylglycoethers,mixtures of polyvalent alcohols with polyfunctional aliphatic amines(e.g., such as diethanolamine, triethanolamine, di-isopropanolamime,etc.), and boric acid or alkali metal borate. Enzyme stabilizationtechniques are additionally disclosed and exemplified in U.S. Pat. Nos.4,261,868, 3,600,319 and European Patent Application Publication No. 0199 405, Application No. 86200586.5, Venegas. Non-boric acid and boratestabilizers are preferred. Enzyme stabilization systems are alsodescribed, for example, in U.S. Pat. Nos. 4,261,868, 3,600,319 and3,519,570.

DETERGENT ADJUNCTS

A wide range of surfactants can be used in the detergent compositions. Atypical listing of anionic, nonionic, ampholytic and zwitterionicclasses, and species of these surfactants, is given in U.S. Pat. No.3,664,961 issued to Norris on May 23, 1972.

Mixtures of anionic surfactants are particularly suitable herein,especially mixtures of sulphonate and sulphate surfactants in a weightratio of from 5:1 to 1:2, preferably from 3:1 to 2:3, more preferablyfrom 3:1 to 1:1. Preferred sulphonates include alkyl benzene sulphonateshaving from 9 to 15, especially 11 to 13 carbon atoms in the alkylradical, and alpha-sulphonated methyl fatty acid esters in which thefatty acid is derived from a C₁₂ -C₁₈ fatty source preferably from a C₁₆-C₁₈ fatty source. In each instance the cation is an alkali metal,preferably sodium. Preferred sulphate surfactants are alkyl sulphateshaving from 12 to 18 carbon atoms in the alkyl radical, optionally inadmixture with ethoxy sulphates having from 10 to 20, preferably 10 to16 carbon atoms in the alkyl radical and an average degree ofethoxylation of 1 to 6. Examples of preferred alkyl sulphates herein aretallow alkyl sulphate, coconut alkyl sulphate, and C₁₄₋₁₅ alkylsulphates. The cation in each instance is again an alkali metal cation,preferably sodium.

One class of nonionic surfactants useful in the present invention arecondensates of ethylene oxide with a hydrophobic moiety to provide asurfactant having an average hydrophilic-lipophilic balance (HLB) in therange from 8 to 17, preferably from 9.5 to 13.5, more preferably from 10to 12.5. The hydrophobic (lipophilic) moiety may be aliphatic oraromatic in nature and the length of the polyoxyethylene group which iscondensed with any particular hydrophobic group can be readily adjustedto yield a water-soluble compound having the desired degree of balancebetween hydrophilic and hydrophobic elements.

Especially preferred nonionic surfactants of this type are the C₉ -C₁₅primary alcohol ethoxylates containing 3-8 moles of ethylene oxide permole of alcohol, particularly the C₁₄ -C₁₅ primary alcohols containing6-8 moles of ethylene oxide per mole of alcohol and the C₁₂ -C₁₄ primaryalcohols containing 3-5 moles of ethylene oxide per mole of alcohol.

Another class of nonionic surfactants comprises alkyl polyglucosidecompounds of general formula

    RO (C.sub.n H.sub.2n O).sub.t Z.sub.x

wherein Z is a moiety derived from glucose; R is a saturated hydrophobicalkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10and n is 2 or 3; x is from 1.3 to 4, the compounds including less than10% unreacted fatty alcohol and less than 50% short chain alkylpolyglucosides. Compounds of this type and their use in detergent aredisclosed in EP-B 0 070 077, 0 075 996 and 0 094 118.

Also suitable as nonionic surfactants are poly hydroxy fatty acid amidesurfactants of the formula ##STR8## wherein R¹ is H, or R¹ is C₁₋₄hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R²is C₅₋₃₁ hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linearhydrocarbyl chain with at least 3 hydroxyls directly connected to thechain, or an alkoxylated derivative thereof. Preferably, R¹ is methyl,R² is a straight C₁₁₋₁₅ alkyl or alkenyl chain such as coconut alkyl ormixtures thereof, and Z is derived from a reducing sugar such asglucose, fructose, maltose, lactose, in a reductive amination reaction.

The compositions according to the present invention may further comprisea builder system. Any conventional builder system is suitable for useherein including aluminosilicate materials, silicates, polycarboxylatesand fatty acids, materials such as ethylenediamine tetraacetate, metalion sequestrants such as aminopolyphosphonates, particularlyethylenediamine tetramethylene phosphonic acid and diethylene triaminepentamethylenephosphonic acid. Though less preferred for obviousenvironmental reasons, phosphate builders can also be used herein.Suitable builders can be an inorganic ion exchange material, commonly aninorganic hydrated aluminosilicate material, more particularly ahydrated synthetic zeolite such as hydrated zeolite A, X, B or HS.Another suitable inorganic builder material is layered silicate, e.g.SKS-6 (Hoechst). SKS-6 is a crystalline layered silicate consisting ofsodium silicate (Na₂ Si₂ O₅).

Suitable polycarboxylates containing one carboxy group include lacticacid, glycolic acid and ether derivatives thereof as disclosed inBelgian Patent Nos. 831,368, 821,369 and 821,370. Polycarboxylatescontaining two carboxy groups include the water-soluble salts ofsuccinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid,diglycollic acid, tartaric acid, tartronic acid and fumaric acid, aswell as the ether carboxylates described in German Offenlegenschrift2,446,686, and 2,446,687 and U.S. Pat. No. 3,935,257 and the sulfinylcarboxylates described in Belgian Patent No. 840,623. Polycarboxylatescontaining three carboxy groups include, in particular, water-solublecitrates, aconitrates and citraconates as well as succinate derivativessuch as the carboxymethyloxysuccinates described in British Patent No.1,379,241, lactoxysuccinates described in Netherlands Application7205873, and the oxypolycarboxylate materials such as2-oxa-1,1,3-propane tricarboxylates described in British Patent No.1,387,447.

Polycarboxylates containing four carboxy groups include oxydisuccinatesdisclosed in British Patent No. 1,261,829, 1,1,2,2-ethanetetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propanetetracarboxylates. Polycarboxylates containing sulfo substituentsinclude the sulfosuccinate derivatives disclosed in British Patent Nos.1,398,421 and 1,398,422 and in U.S. Pat. No. 3,936,448, and thesulfonated pyrolysed citrates described in British Patent No. 1,082,179,while polycarboxylates containing phosphone substituents are disclosedin British Patent No. 1,439,000.

Alicyclic and heterocyclic polycarboxylates includecyclopentane-cis,cis,cis-tetracarboxylates, cyclopentadienidepentacarboxylates, 2,3,4,5-tetrahydrofuran-cis, cis,cis-tetracarboxylates, 2,5-tetrahydrofuran-cis-dicarboxylates,2,2,5,5-tetrahydrofuran-tetracarboxylates,1,2,3,4,5,6-hexane-hexacarboxylates and and carboxymethyl derivatives ofpolyhydric alcohols such as sorbitol, mannitol and xylitol. Aromaticpolycarboxylates include mellitic acid, pyromellitic acid and thephtalic acid derivatives disclosed in British Patent No. 1,425,343.

Of the above, the preferred polycarboxylates are hydroxycarboxylatescontaining up to three carboxy groups per molecule, more particularlycitrates. Preferred builder systems for use in the present compositionsinclude a mixture of a water-insoluble aluminosilicate builder such aszeolite A or of a layered silicate (sks/6), and a water-solublecarboxylate chelating agent such as citric acid.

A suitable chelant for inclusion in the detergent compositions inaccordance with the invention is ethylenediamine-N,N'-disuccinic acid(EDDS) or the alkali metal, alkaline earth metal, ammonium, orsubstituted ammonium salts thereof, or mixtures thereof. Preferred EDDScompounds are the free acid form and the sodium or magnesium saltthereof. Examples of such preferred sodium salts of EDDS include Na₂EDDS and Na₄ EDDS. Examples of such preferred magnesium salts of EDDSinclude MgEDDS and Mg₂ EDDS. The magnesium salts are the most preferredfor inclusion in compositions in accordance with the invention.

Especially for the liquid execution herein, suitable fatty acid buildersfor use herein are saturated or unsaturated C10-18 fatty acids, as wellas well as the corresponding soaps. Preferred saturated species havefrom 12 to 16 carbon atoms in the alkyl chain. The preferred unsaturatedfatty acid is oleic acid.

Preferred builder systems for use in granular compositions include amixture of a water-insoluble aluminosilicate builder such as zeolite A,and a watersoluble carboxylate chelating agent such as citric acid.

Other builder materials that can form part of the builder system for usein granular compositions the purposes of the invention include inorganicmaterials such as alkali metal carbonates, bicarbonates, silicates, andorganic materials such as the organic phosphonates, amiono polyalkylenephosphonates and amino polycarboxylates.

Other suitable water-soluble organic salts are the homo- or copolymericacids or their salts, in which the polycarboxylic acid comprises atleast two carboxyl radicals separated from each other by not more thantwo carbon atoms.

Polymers of this type are disclosed in GB-A-1,596,756. Examples of suchsalts are polyacrylates of MW 2000-5000 and their copolymers with maleicanhydride, such copolymers having a molecular weight of from 20,000 to70,000, especially about 40,000.

Detergency builder salts are normally included in amounts of from 10% to80% by weight of the composition preferably from 20% to 70% and mostusually from 30% to 60% by weight.

Detergent ingredients that can be included in the detergent compositionsof the present invention include bleaching agents. These bleaching agentcomponents can include one or more oxygen bleaching agents and,depending upon the bleaching agent chosen, one or more bleachactivators. When present bleaching compounds will typically be presentat levels of from about 1% to about 10%, of the detergent composition.In general, bleaching compounds are optional components in non-liquidformulations, e.g. granular detergents. If present, the amount of bleachactivators will typically be from about 0.1% to about 60%, moretypically from about 0.5% to about 40% of the bleaching composition.

The bleaching agent component for use herein can be any of the bleachingagents useful for detergent compositions including oxygen bleaches aswell as others known in the art.

In a method aspect, this invention further provides a method forcleaning fabrics, fibers, textiles, at temperatures below about 50° C.,especially below about 40° C., with a detergent composition containingpolyamine N-oxide containing polymers, optional auxiliary detersivesurfactants, optional detersive adjunct ingredients, and a bleachingagent.

The bleaching agent suitable for the present invention can be anactivated or non-activated bleaching agent.

One category of oxygen bleaching agent that can be used encompassespercarboxylic acid bleaching agents and salts thereof. Suitable examplesof this class of agents include magnesium monoperoxyphthalatehexahydrate, the magnesium salt of meta-chloro perbenzoic acid,4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid.Such bleaching agents are disclosed in U.S. Pat. No. 4,483,781, U.S.patent application Ser. No. 740,446, European Patent Application0,133,354 and U.S. Pat. No. 4,412,934. Highly preferred bleaching agentsalso include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S.Pat. No. 4,634,551.

Another category of bleaching agents that can be used encompasses thehalogen bleaching agents. Examples of hypohalite bleaching agents, forexample, include trichloro isocyanuric acid and the sodium and potassiumdichloroisocyanurates and N-chloro and N-bromo alkane sulphonamides.Such materials are normally added at 0.5-10% by weight of the finishedproduct, preferably 1-5% by weight.

Preferably, the bleaches suitable for the present invention includeperoxygen bleaches. Examples of suitable water-soluble solid peroxygenbleaches include hydrogen peroxide releasing agents such as hydrogenperoxide, perborates, e.g. perborate monohydrate, perboratetetrahydrate, persulfates, percarbonates, peroxydisulfates,perphosphates and peroxyhydrates. Preferred bleaches are percarbonatesand perborates.

The hydrogen peroxide releasing agents can be used in combination withbleach activators such as tetraacetylethylenediamine (TAED),nonanoyloxybenzenesulfonate (NOBS, described in U.S. Pat. No.4,412,934), 3,5,-trimethylhexanoloxybenzenesulfonate (ISONOBS, describedin EP 120,591) or pentaacetylglucose (PAG), which are perhydrolyzed toform a peracid as the active bleaching species, leading to improvedbleaching effect. Also suitable activators are acylated citrate esterssuch as disclosed in Copending European Patent Application No.91870207.7.

The hydrogen peroxide may also be present by adding an enzymatic system(i.e. an enzyme and a substrate therefore) which is capable ofgenerating hydrogen peroxide at the beginning or during the washingand/or rinsing process. Such enzymatic systems are disclosed in EPPatent Application 91202655.6 filed Oct. 9, 1991.

Other peroxygen bleaches suitable for the present invention includeorganic peroxyacids such as percarboxylic acids.

Bleaching agents other than oxygen bleaching agents are also known inthe art and can be utilized herein. One type of non-oxygen bleachingagent of particular interest includes photoactivated bleaching agentssuch as the sulfonated zinc and/or aluminum phthalocyanines. Thesematerials can be deposited upon the substrate during the washingprocess. Upon irradiation with light, in the presence of oxygen, such asby hanging clothes out to dry in the daylight, the sulfonated zincphthalocyanine is activated and, consequently, the substrate isbleached. Preferred zinc phthalocyanine and a photoactivated bleachingprocess are described in U.S. Pat. No. 4,033,718. Typically, detergentcompositions will contain about 0.025% to about 1.25%, by weight, ofsulfonated zinc phthalocyanine.

Other suitable detergent ingredients that can be added are enzymeoxidation scavengers which are described in Copending European Patentaplication N 92870018.6 filed on Jan. 31, 1992. Examples of such enzymeoxidation scavengers are ethoxylated tetraethylene polyamines.Especially preferred detergent ingredients that can be added aretechnologies which also provide a type of color care benefit. Examplesof these technologies are metallo catalysts for color maintancerejuvenation. Such metallo catalysts are described in copending EuropeanPatent Application No. 92870181.2.

In addition, it has been found that the polyamine-N-oxide containingpolymers eliminate or reduce the deposition of the metallo-catalyst ontothe fabrics resulting in improved whiteness benefit.

Another optional ingredient is a suds suppressor, exemplified bysilicones, and silica-silicone mixtures. Silicones can be generallyrepresented by alkylated polysiloxane materials while silica is normallyused in finely divided forms exemplified by silica aerogels and xerogelsand hydrophobic silicas of various types. These materials can beincorporated as particulates in which the suds suppressor isadvantageously releasably incorporated in a water-soluble orwater-dispersible, substantially non-surface-active detergentimpermeable carrier. Alternatively the suds suppressor can be dissolvedor dispersed in a liquid carrier and applied by spraying on to one ormore of the other components.

A preferred silicone suds controlling agent is disclosed in Bartollotaet al. U.S. Pat. No. 3,933,672. Other particularly useful sudssuppressors are the self-emulsifying silicone suds suppressors,described in German Patent Application DTOS 2 646 126 published Apr. 28,1977. An example of such a compound is DC-544, commercially availablefrom Dow Corning, which is a siloxane-glycol copolymer. Especiallypreferred suds controlling agent are the suds suppressor systemcomprising a mixture of silicone oils and 2-alkyl-alcanols. Suitable2-alkyl-alcanols are 2-butyl-octanol which are commercially availableunder the trade name Isofol 12 R.

Such suds suppressor system are described in Copending European Patentapplication N 92870174.7 filed 10 Nov. 1992.

Especially preferred silicone suds controlling agents are described inCopending European Patent application No. 92201649.8 Said compositionscan comprise a silicone/silica mixture in combination with fumednonporous silica such as Aerosil^(R).

The suds suppressors described above are normally employed at levels offrom 0.001% to 2% by weight of the composition, preferably from 0.01% to1% by weight.

Other components used in detergent compositions may be employed, such assoil-suspending agents soil-release agents, optical brighteners,abrasives, bactericides, tarnish inhibitors, coloring agents andencapsulated and/or non-encapsulated perfumes.

Antiredeposition and soil suspension agents suitable herein includecellulose derivatives such as methylcellulose, carboxymethylcelluloseand hydroxyethylcellulose, and homo- or co-polymeric polycarboxylicacids or their salts. Polymers of this type include the polyacrylatesand maleic anhydride-acrylic acid copolymers previously mentioned asbuilders, as well as copolymers of maleic anhydride with ethylene,methylvinyl ether or methacrylic acid, the maleic anhydride constitutingat least 20 mole percent of the copolymer. These materials are normallyused at levels of from 0.5% to 10% by weight, more preferably from 0.75%to 8%, most preferably from 1% to 6% by weight of the composition.

Preferred optical brighteners are anionic in character, examples ofwhich are disodium 4,4¹-bis-(2-diethanolamino-4-anilino-s-triazin-6-ylamino)stilbene-2:2¹disulphonate, disodium 4,-4¹-bis-(2-morpholino-4-anilino-s-triazin-6-ylamminostilbene-2:2¹-disulphonate, disodium 4,4¹-bis-(2,4-dianilino-s-triazin-6-ylamino)stilbene-2:2¹ -disulphonate,monosodium 4¹,4¹¹-bis-(2,4-dianilino-s-triazin-6ylamino)stilbene-2-sulphonate, disodium4,4¹-bis-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-s-triazin-6-ylamino)stilbene-2,2¹-disulphonate, disodium 4,4¹-bis-(4-phenyl-2,1,3-triazol-2-yl)-stilbene-2,2¹ disulphonate, disodium4,4¹bis(2-anilino-4--(1-methyl-2-hydroxyethylamino)-s-triazin-6-ylamino)stilbene-2,2¹ disulphonate and sodium 2(stilbyl-4¹¹ -(naphtho-1¹,2¹:4,5)-1,2,3-triazole-2¹¹ -sulphonate.

Other useful polymeric materials are the polyethylene glycols,particularly those of molecular weight 1000-10000, more particularly2000 to 8000 and most preferably about 4000. These are used at levels offrom 0.20% to 5% more preferably from 0.25% to 2.5% by weight. Thesepolymers and the previously mentioned homo- or co-polymericpolycarboxylate salts are valuable for improving whiteness maintenance,fabric ash deposition, and cleaning performance on clay, proteinaceousand oxidizable soils in the presence of transition metal impurities.

Soil release agents useful in compositions of the present invention areconventionally copolymers or terpolymers of terephthalic acid withethylene glycol and/or propylene glycol units in various arrangements.Examples of such polymers are disclosed in the commonly assigned U.S.Pat. Nos. 4,116,885 and 4,711,730 and European Published PatentApplication No. 0 272 033. A particular preferred polymer in accordancewith EP-A-0 272 033 has the formula ##STR9## where PEG is --(OC₂H₄)O--,PO is (OC₃ H₆ O) and T is (pcOC₆ H₄ CO).

Also very useful are modified polyesters as random copolymers ofdimethyl terephtalate, dimethyl sulfoisophtalate, ethylene glycol and1-2 propane diol, the end groups consisting primarily of sulphobenzoateand secondarily of mono esters of ethylene glycol and/or propane-diol.The target is to obtain a polymer capped at both end by sulphobenzoategroups, "primarily", in the present context most of said copolymersherein will be end-capped by sulphobenzoate groups. However, somecopolymers will be less than fully capped, and therefore their endgroups may consist of monoester of ethylene glycol and/or propane 1-2diol, thereof consist "secondarily" of such species.

The selected polyesters herein contain about 46% by weight of dimethylterephtalic acid, about 16% by weight of propane -1.2 diol, about 10% byweight ethylene glycol about 13% by weight of dimethyl sulfobenzoid acidand about 15% by weight of sulfoisophtalic acid, and have a molecularweight of about 3,000. The polyesters and their method of preparationare described in detail in EPA 311 342.

The detergent compositions according to the invention can be in liquid,paste, gels or granular forms. Granular compositions according to thepresent invention can also be in "compact form", i.e. they may have arelatively higher density than conventional granular detergents, i.e.from 550 to 950 g/l; in such case, the granular detergent compositionsaccording to the present invention will contain a lower amount of"inorganic filler salt", compared to conventional granular detergents;typical filler salts are alkaline earth metal salts of sulphates andchlorides, typically sodium sulphate; "compact" detergents typicallycomprise not more than 10% filler salt. The liquid compositionsaccording to the present invention can also be in "concentrated form",in such case, the liquid detergent compositions according to the presentinvention will contain a lower amount of water, compared to conventionalliquid detergents. Typically, the water content of the concentratedliquid detergent is less than 30%, more preferably less than 20%, mostpreferably less than 10% by weight of the detergent compositions. Otherexamples of liquid compositions are anhydrous compositions containingsubstantially no water. Both aqueous and non-aqueous liquid compositionscan be structured or non-structured.

The present invention also relates to a process for inhibiting dyetransfer from one fabric to another of solubilized and suspended dyesencountered during fabric laundering operations involving coloredfabrics.

The process comprises contacting fabrics with a laundering solution ashereinbefore described.

The process of the invention is conveniently carried out in the courseof the washing process. The washing process is preferably carried out at5° C. to 75° C., especially 20 to 60, but the polymers are effective atup to 95° C. and higher temperatures. The pH of the treatment solutionis preferably from 7 to 11, especially from 7.5 to 10.5.

The process and compositions of the invention can also be used asdetergent additive products. Such additive products are intended tosupplement or boost the performance of conventional detergentcompositions.

The detergent compositions according to the present invention includecompositions which are to be used for cleaning substrates, such asfabrics, fibers, hard surfaces, skin etc., for example hard surfacecleaning compositions (with or without abrasives), laundry detergentcompositions, automatic and non automatic dishwashing compositions.

The following examples are meant to exemplify compositions of thepresent invention, but are not necessarily meant to limit or otherwisedefine the scope of the invention, said scope being determined accordingto claims which follow.

A liquid detergent composition according to the present invention isprepared, having the following compositions:

                  TABLE I                                                         ______________________________________                                        % by weight of the total detergent composition                                ______________________________________                                        Linear alkylbenzene sulfonate                                                                        10                                                     Alkyl sulphate         4                                                      Fatty alcohol (C.sub.12 -C.sub.15) ethoxylate                                                        12                                                     Fatty acid             10                                                     Oleic acid             4                                                      Citric acid            1                                                      NaOH                   3.4                                                    Propanediol            1.5                                                    Ethanol                10                                                     ______________________________________                                    

EXAMPLE I

The extent of dye transfer from different colored fabrics was studiedusing a launder-o-meter test that simulates a 30 min wash cycle. Thelaunder-o-meter beaker contains 200 ml of a detergent solution, a 10cm×10 cm piece of the colored fabric and a multifiber swatch which isused as a pick-up tracer for the bleeding dye. The multifiber swatchconsists of 6 pieces (1.5 cm×5 cm each) of different material(polyacetate, cotton, polyamide, polyester, wool and orlon) which aresewn together.

The extent of dye transfer is assessed by a Hunter Colour measurement.The Hunter Colour system evaluates the colour of a fabric sample interms of the ΔE value which represents the change in the Hunter L, a,b,values which are determined by reflecting spectrometrie. The ΔE valueis defined by the following equation:

    ΔE={(a.sub.f -a.sub.i).sup.2 +(b.sub.f -b.sub.i).sup.2 +(L.sub.f -L.sub.i).sup.2 }.sup.1/2

where the subscripts i and f refer to the Hunter value before and afterwashing in the presence of the bleeding fabric, respectively. The leastsignificant difference is 1 at 95% confidence level.

Experimental conditions:

Example I demonstrates the increased dye transfer inhibiting performanceof the combination of polyamine-N-oxide containing polymers (PVNO :poly(4-vinylpyridine-N-oxide) which has an average molecular weight ofabout 10,000 and an amine to amine N-oxide ratio of 1:10 (determined byNMR)) and peroxidase.

The extent of dye transfer from different colored fabrics was studiedusing a launder-o-meter test that simulates a 30 min wash cycle. Thelaunder-o-meter beaker contains 0.7% of the detergent composition, a 10cm×10 cm piece of the colored fabric and a multifiber swatch which isused as a pick-up tracer for the bleeding dye. The multifiber swatchconsists each of cotton.

A set of two realistic bleeding fabrics (50 cm² of each) were washedtogether with a multifiber pick-up tracer in a launderometer for 30 min.In a first launderometer pot (Test A), the detergent solution did notcontain any dye transfer inhibiting agent. The second pot contained 10ppm PVNO (Test B). The third pot contained 7 peroxidase (ex-Novo)Units/ml of wash solution (Test C). Also added are 10 ppm glucose and0.1 units of Glox/ml to generate oxygen which is necessary to activatethe Peroxidase. Finally the fourth pot contains the peroxidase systemand PVNO (Test D).

                  TABLE                                                           ______________________________________                                        Level of dye transfer reduction by PVNO, Peroxidase and                       the combination (ΔE values).                                            pH = 7.8/Washing temperature 40° C.                                    Bleeding fabric                                                                          Bleeding fabric                                                    composition                                                                              color        A       B    C    D                                   ______________________________________                                        100% cotton                                                                              Direct blue 90                                                                             21.0    14.8 12.1 2.7                                 ______________________________________                                    

EXAMPLE II

A liquid detergent composition according to the present invention isprepared, having the following compositions:

    ______________________________________                                        % by weight of the total detergent composition                                                   A    B      C      D                                       ______________________________________                                        Linear alkylbenzene sulfonate                                                                      10     10     10   10                                    Alkyl sulphate       4      4      4    4                                     Fatty alcohol (C.sub.12 -C.sub.15) ethoxylate                                                      12     12     12   12                                    Fatty acid           10     10     10   10                                    Oleic acid           4      4      4    4                                     Citric acid          1      1      1    1                                     Diethylenetriaminepentamethylene                                                                   1.5    1.5    1.5  1.5                                   Phosphonic acid                                                               NaOH                 3.4    3.4    3.4  3.4                                   Propanediol          1.5    1.5    1.5  1.5                                   Ethanol              10     10     10   10                                    Ethoxylated tetraethylene pentamine                                                                0.7    0.7    0.7  0.7                                   Poly(4-vinylpyridine)-N-oxide                                                                      0-1    0-1    0-1  0-1                                   Thermamyl            0.13   --     0.13 0.13                                  Carezyme             0.01   0.01   --   0.01                                  FN-Base              1.8    1.8    1.8  --                                    Lipolase             0.14   0.14   0.14 0.14                                  Endoglucanase A      0.53   0.53   --   0.53                                  Suds supressor (ISOFOL.sup.r)                                                                      2.5    2.5    2.5  2.5                                   Minors               up to 100                                                ______________________________________                                    

EXAMPLE III

A compact granular detergent composition according to the presentinvention is prepared, having the following formulation:

    ______________________________________                                        % by weight of the total detergent composition                                                   A    B      C      D                                       ______________________________________                                        Linear alkyl benzene sulphonate                                                                    11.40  11.40  11.40                                                                              11.40                                 Tallow alkyl sulphate                                                                              1.80   1.80   1.80 1.80                                  C.sub.45 alkyl sulphate                                                                            3.00   3.00   3.00 3.00                                  C.sub.45 alcohol 7 times ethoxylated                                                               4.00   4.00   4.00 4.00                                  Tallow alcohol 11 times ethoxylated                                                                1.80   1.80   1.80 1.80                                  Dispersant           0.07   0.07   0.07 0.07                                  Silicone fluid       0.80   0.80   0.80 0.80                                  Trisodium citrate    14.00  14.00  14.00                                                                              14.00                                 Citric acid          3.00   3.00   3.00 3.00                                  Zeolite              32.50  32.50  32.50                                                                              32.50                                 Maleic acid acrylic acid copolymer                                                                 5.00   5.00   5.00 5.00                                  Perborate            0.5    0.5    0.5  0.5                                   Cellulase (active protein)                                                                         0.03   0.2    --   0.2                                   Alkalase/BAN         0.60   --     0.6  0.6                                   Lipase               0.36   0.36   0.36 --                                    Peroxidase           0.4    --     0.4  0.4                                   Sodium silicate      2.00   2.00   2.00 2.00                                  Sodium sulphate      3.50   3.50   3.50 3.50                                  Poly(4-vinylpyridine)-N-oxide                                                                      0-1    0-1    0-1  0-1                                   Minors               up to 100                                                ______________________________________                                    

The above compositions (Example II and III) were very good at displayingexcellent cleaning and detergency performance with outstandingcolor-care performance on colored fabrics and mixed loads of colored andwhite fabrics.

We claim:
 1. A dye transfer inhibiting detergent compositioncomprisinga) poly(4-vinylpyridine-N-oxide) having a ratio of amine toamine N-oxide of from about 2:3 to about 1:1,000,000; and ##STR10####STR11## b) a cleaning effective amount of an enzyme.
 2. A dye transferinhibiting composition according to claim 1 wherein thepoly(4-vinylpyridine-N-oxide) polymer has an average molecular weightwithin the range of 500 to 1,000,000.
 3. A dye transfer inhibitingcomposition according to claim 1 wherein thepoly(4-vinylpyridine-N-oxide) is present at levels from 0.001 to 10% byweight of the composition.
 4. A dye transfer inhibiting compositionaccording to claim 1 wherein said enzyme is selected from the groupconsisting of cellulases, peroxidases, lipases, amylases, or mixturesthereof.
 5. A dye transfer inhibiting compositions according to claim 1wherein said enzyme is a cellulase or a peroxidase or a mixture thereof.6. A detergent composition which comprises a dye transfer inhibitingcomposition according to claim 1 further comprising surfactants,builders chelants, bleaching agents, soil-suspending agents, sudssuppressors soil release agents, optical brighteners, abrasives,bactericides, tarnish inhibitors, coloring agents, perfumes, or mixturesthereof.
 7. A dye transfer inhibiting composition in the form of anon-dusting granule or a liquid detergent additive; said compositioncomprises:a) poly(4-vinylpyridine-N-oxide) having a ratio of amine toamine N-oxide of from about 2:3 to about 1:1,000,000;and b) a cleaningeffective amount of an enzyme.
 8. A detergent composition whichcomprises a dye transfer inhibiting composition according to claim 7further comprising surfactants, builders, chelants, bleaching agents,soil-suspending agents, suds suppressor, soil release agents, opticalbrighteners, abrasives, bactericides, tarnish inhibitors, coloringagents, perfumes, or mixtures thereof.